CN1685076A - Plasma treated metallized films - Google Patents
Plasma treated metallized films Download PDFInfo
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- CN1685076A CN1685076A CN 03823166 CN03823166A CN1685076A CN 1685076 A CN1685076 A CN 1685076A CN 03823166 CN03823166 CN 03823166 CN 03823166 A CN03823166 A CN 03823166A CN 1685076 A CN1685076 A CN 1685076A
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- plasma
- cement composite
- composite treated
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- 239000011104 metalized film Substances 0.000 title claims description 15
- 239000002985 plastic film Substances 0.000 claims abstract description 8
- 229920006255 plastic film Polymers 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 157
- 238000000034 method Methods 0.000 claims description 104
- 239000004568 cement Substances 0.000 claims description 97
- 239000002131 composite material Substances 0.000 claims description 97
- 229920003023 plastic Polymers 0.000 claims description 59
- 239000004033 plastic Substances 0.000 claims description 57
- 238000001465 metallisation Methods 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 16
- 230000005540 biological transmission Effects 0.000 claims description 13
- 239000004677 Nylon Substances 0.000 claims description 11
- 229920001778 nylon Polymers 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 238000001704 evaporation Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 10
- 238000012856 packing Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000006200 vaporizer Substances 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FAIFRACTBXWXGY-JTTXIWGLSA-N COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 Chemical compound COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 FAIFRACTBXWXGY-JTTXIWGLSA-N 0.000 description 1
- 101150031456 MDGA2 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
A plasma treated metallized plastic film of ultra high barrier properties is provided at low cost.
Description
Related application
The application requires the U.S. Provisional Application 60/403,294 submitted on August 14th, 2002, and the right of priority of the U.S. Provisional Application of submitting on February 13rd, 2,003 60/448,859, its in full reference in content be incorporated into this.
Invention field
The present invention relates to metalized film, be particularly useful for grain and liquid packaging and decorative balloons industry.
Background of invention
The present invention broadly relates to various types of metallized plastic films.Types of metallized plastic films is known in the art, and is used to provide the barrier between packing or product internal and external environment.Such barrier can be used for for example grain and liquid packaging, or is used for decorative balloons.In grain and liquid situation, pack the product of the barrier protection packaging that provides by this film, can not lose the freshness and the local flavor of food, prevent that promptly block and water vapor can enter packing and/or product is exposed in the UV-light.Similarly, in case of balloons, this barrier can provide protection, in case the gas in the balloon goes out by film diffusion, causes that gas do not wish the loss that takes place, and this diffusion can cause the contraction and the lost of life of balloon.
The sixties are early stage, with the food product pack of various transparent plastic films as flexibility.Such transparent film for example can print, and with stacked as the packing inner layer polyethylene, polyethylene also is used for improving stopping property.Yet, because transparent plastic film does not possess the gas and the moisture barrier characteristic that can satisfy suitable packing instructions, so proposed metalized film in early days at the seventies subsequently.Metallization processes carries out at a vacuum chamber, and in vacuum chamber, metal (as fine aluminium) fusing, evaporation are deposited on the surface of film then.When using aluminium, for example, steam is deposited on substrate surface, stays the metallic aluminium coating of very thin (as 10-1000 ), and it is enough to the surface pore of sealing substrate.Sedimentary metal can prevent that oxygen and water vapor are delivered to the inside of packing from outside atmosphere, have just improved barrier properties.
But the technology that further develops thereafter relates to the chemical constitution of change metalized surface.The modification of these surface aggregate things has also improved the barrier action to moisture and gas except improving the metal tackiness.Surface modification can be that atmosphere is handled (comprising corona, flame, chemistry and Cement Composite Treated by Plasma), and these are handled at substrate surface and produce direct oxidation.Most surface is bathed and is carried out modification and be not penetrated into material body at the top surface to polymer composition.Must pay close attention to, decide the method for various types of membranes being carried out best surface modification, to satisfy the desired final performance of product.
Yet there are two class main drawbacks in various surface treatments.The first, find that processing value descends in time from finish surface treatment to metallizing vacuum chamber.Because rolls stores with the winding form, surface energy is owing to the surface that some chemical groups are diffused into film descends.In addition, the final price that additional procedure has increased film is used in surface treatment.
Therefore, the advantage of this area is provided a kind of improved treatment process and improved metallized product, this product can be made with simple and cheap method, and has the barrier properties that has improved, and is useful in this area.The advantage that also has provides the method that can use on planar film, and various surface-treated advantages are provided, not waste, and cost is low, and these also are useful.
Summary of the invention
The purpose of this invention is to provide a kind of packing film that has improved the barrier properties of oxygen and water vapor transmission that has.
Another object of the present invention provides a kind of packing film that has improved the UV-light barrier properties that has.
The present invention have a purpose provide a kind of have improved barrier properties, and can be easy and hang down the packing film of manufacturing with becoming.
According to the present invention, a kind of plasma body metalized film is provided, can be applicable to grain and liquid packaging and balloon industry especially.This film compares with the film of prior art, has the barrier characteristics that has improved, simultaneously can easy and low-cost manufacturing.In a better embodiment, the method that provides is that plastics film carries out Cement Composite Treated by Plasma at the vacuum chamber of a metallization apparatus, and applies required coating material (as aluminum vapor) at the one or both sides of treated film.By method and condition in this announcement, the film of manufacturing has good oxygen and water vapor barrier properties.Because the barrier properties that these have improved, in the pleasing aesthetic appearance that keeps metalized film, aspect advertisement for foods distribution and decorative balloons product, tangible advantage is arranged in, obviously prolongs life and balloon flotation time.
Detailed description of the Invention
According to the present invention, the method for the film of the barrier properties that provides a kind of manufacturing to have to improve.Particularly, this film has improved the barrier to oxygen and water vapor transmission and UV-light.The present invention also provides a kind of improved barrier, provides easy simultaneously and makes the method for film at low cost.In better embodiment, this film can be used for the packaging industry of food and liquid, or is used for decorative balloons.
The method according to this invention, the user is generally from roll of plastic, and the thickness of plastics sheet, width and length can change according to user's ultimate demand in the volume.For example, initial film can be the film of polyester, polypropylene, polyethylene, polyvinyl chloride or nylon.Be the processing form that initial processing film is become to require, film is handled in the equipment of vacuum system, is used for coating material is deposited on this film.In the better embodiment of the present invention, be Galileo Vacuum System equipment, be more preferably Galileo Mega2 model, as Mega 4-2410B to thin film metallized used device.Yet, though with back one equipment conduct the present invention is described in the explanation of better embodiment, should understand the present invention and be not limited to equipment disclosed here or better embodiment at this, also can use other vacuum metallization processes equipment.
In a vacuum system metallization apparatus, be used for the various parts of film processing and metallized film are comprised, for example, winding system, vacuum chamber, pumping system, Controlling System, vapo(u)rization system etc.Roll of plastic is partly imported by the winding system of equipment, and this part comprises drive system, tension control system etc.Vacuum chamber is the part of this equipment, is provided at the vacuum that needs usefulness in the coating procedure, and it has vaporizer, is used for coating material is flashed to gas, is deposited on the film.Gas pump in the equipment is undertaken by pumping installation.
Film rolling is assemblied in the metallization equipment, is placed on the part that is called " axis of dilatation ", and film is from rolling up expansion, in order to the rest part by equipment.Film, makes film finally by the plasma processor on other rollers, and by evaporating area, arrives again on the hollow of axle (twining point apparatus again) up to film by equipment from axis of dilatation.This process is wrapped in winding system partly from transparent film.After installing, closing device seals and is hedged off from the outer world the pumping process of beginning vacuum pump.During bleeding, remove all air from vacuum chamber, up to meet the requirements of condition of high vacuum degree (for example, in a preferred embodiment, better to 10
-5-7.0 * 10
-5The mbar scope).
In case after equipment reaches vacuum pressure, can carry out Cement Composite Treated by Plasma.As discussed above, Cement Composite Treated by Plasma relates to the modification on plastics film surface, is used for improving the tackiness of coating material (as metal) and surface film.In addition, Cement Composite Treated by Plasma can improve the barrier properties to moisture and gas of the metalized film of making.In plasma processor, provide high voltage power (better 7-25KW), upfield and a kind of gaseous mixture.The preferred operations condition of the metalized film that preparation the present invention needs, and various thin-film material is listed in the table below 1.
The principal character of Cement Composite Treated by Plasma is that it provides high-energy electron, presents in an amount at least sufficient to produce heavy ion, and the adding of these electronics is from the gaseous mixture to the film surface bombardment.According to the present invention, the preferred gas mixture that is used for Cement Composite Treated by Plasma is the mixture of 80% nitrogen and 20% argon gas (" the gas B " of table 1 is also referred to as " plasma body B ").Perhaps, can use the gaseous mixture of 30% oxygen and 70% argon gas, or the gaseous mixture of 50% oxygen and 50% argon gas.Can also use in argon gas, nitrogen and/or the oxygen one or more, or single scrubbed gas or be suitable for the mixture of arbitrary combination of the application of requirement.Some other gas also can be used for handling film surface, as long as they can be suitable for providing the final response of the film needs that obtained.
When using plasma generator, ion and electronics are limited in the magnetic field above the plasma generator, and this moment, film was by this producer.Permanent magnet can also be placed on film back, strengthen some systems, allow magnetic line of force open towards film with magnetic methods by treater.These permanent magnets have ion and the electronics effect to the film surface motion of ordering about.
Electric system is transported to plasma processor with gaseous mixture and combines, and can clean and activate film surface, to carry out chemical modification.This variation of surface property just occurs in before coating material (as the aluminum vapor) deposition.Can think to have produced oxygen species on the film surface below metal level, cause the oxidation on surface.Oxygen or be added on the surface by gas, or be attracted on the surface from polymkeric substance itself.
The zone that is positioned in equipment before the evaporating area is provided with the plasma treatment device, and it and evaporating area sealing separate.Film moves to evaporating area by behind the plasma processor.Plasma processor and evaporating area separate, and make the gas of plasma processor can not be subjected to the interference of evaporative process.
After film is handled with plasma processor, enter and by evaporating area through the film of Cement Composite Treated by Plasma, vaporizer fusing also evaporation will be applied to coating material on the film.In evaporating area, solid coating material (as the coating material of aluminum steel or other any needs) is sent into vaporizer, when vaporizer is heated to the temperature that needs (, being 1400 ℃) as in the aluminium situation, the coating material evaporation.
Although the inventive method can be carried out with the speed of any needs, in embodiment preferably, equipment is activated, withdrawing gas meets the requirements of vacuum tightness, simultaneously provide energy to plasma processor, heating fumigators begins mobile film in equipment afterwards to the temperature that needs.Like this,, can make film move through entire equipment rapidly and effectively, need not in a part, to wait by the time next section is prepared to come into operation in case the equipment each several part is ready.Usually need to wait for several minutes and send into all evaporators (being also referred to as " boat "), and filled all holes in the pottery up to coating material up to coating material, and evenly evaporation of beginning, afterwards, film begins to move through metallization equipment.In other words, be preferably, before beginning with plasma processor processing film, heating fumigators also makes all boats stable, and like this, film can be from plasma processor by entering evaporating area and moving forward immediately.
Therefore, be in evaporating area, the film after Cement Composite Treated by Plasma contacts with coating material.The temperature of vaporizer depends on the material of needs evaporation.In a better embodiment, fine aluminium deposits at for example about 1400 ℃ of start vaporizers.In another embodiment, can use silver or gold or tin or other metals, perhaps glass (as silicon oxide).Therefore, although general with the example of aluminium in the explanation of this paper, should be understood that the present invention is not subjected to the restriction of these preferred materials as better embodiment.
In evaporation step, move in the evaporating area of the molecule of coating material under whole vacuum.For meeting the requirements of vacuum, pump is inhaled device be connected with evaporating area, improve at this regional coating procedure.For example, in the situation of aluminium, importantly aluminium does not contact with oxygen molecule because must be sedimentary on film be fine aluminium, it is very unfavorable having aluminum oxide.Equally, aluminium can seethe with excitement under lower pressure and more effective evaporation.Vacuum also help the aluminium molecule from film on one side to the other side, uniform coating is provided, on film, can not produce deep mixed zone.In addition, extract oxygen out help avoid ceramic evaporator infringement, (moving under about 1400 ℃ or higher temperature) can make vaporizer decompose on every side because oxygen molecule exists in high-temperature evaporator, thereby shortens its useful life.
In vacuo, aluminium contacts the surface of the plastics film that may pass through on cold roller.Cold roller remains on enough low temperature, can keep dimensional stability when making plastics film be subjected to the excessive heat of steam, is more preferably, and film is remained on enough low temperature, can promote the aluminium condensation in the above.For example, when steam was about 1400 ℃, film can remain on about 70-80 °F.
Although the highstrung film of heat is needed cold roller, cold roller is not essential to this method.Some film is heat-resisting, therefore needn't cool off specially.To these films, the cold temperature itself of the envrionment temperature of film or vacuum just can provide enough temperature difference to cause condensation, and film moves with fast linear velocity, and the time also makes film melts inadequately.Equally, during evaporating, film need not to support with cold roller, but unsettled getting final product promptly, metallized when moving between two rollers.If film is unsettled, can after evaporation step, cool off, if desired, can use cold roller or pass through cooling tower.
When the coating material steam when film on the roller contacts, coating material is condensation on film surface.After the contact, Chemical bond and physical bond effect take place between aluminium and film.The material coating of adequate thickness just is provided on base material, the surface pore on the base material is sealed.In this better embodiment, for example, use the coating of 120-200 , be more preferably 10-1000 , but if desired, can adopt the thickness of any other requirement.For example, in these embodiments, can use laminated coating, obtain the coating of bigger thickness,, that is, improve barrier properties, but cost be higher with further reduction oxygen or this material of steam permeable at surperficial one or both sides.
Al deposition on film after, film again on the fuse of sky, is made the product volume.After this volume is finished, close evacuating valve, cut off evaporators, open air inlet valve, allow more air admission equipment, big to reach normal atmosphere.At this moment, open equipment, take out the product volume of making.
Barrier properties and the adhesive raising degree of metal are depended on reaction conditions, for example, the gas of use, mixture ratio and flow.Therefore, according to the present invention, worked out the reaction conditions that obtains best barrier properties.According to the present invention, be listed in the table below in 1 with the preferred reaction conditions of the improved metallized film of dissimilar thin film fabrication.
Table 1
| Table 1: the reaction conditions of plasma body method for metallising | |||||||||
| Film type | Thickness | ??MOS ??/MBS | Gas | Flow velocity cm 3/s | Power KW | Linear velocity ft/m | Drum temperature | Vacuum mbar | Optical density(OD) |
| Nylon | ??40 | ??MOS | ??B | ??500 | ??10 | ??1400 | ??-4 | ?7.0E-005 | ????2.6 |
| Nylon | ??48 | ??MOS | ??B | ??500 | ??10 | ??1400 | ??-4 | ?7.0E-005 | ????2.6 |
| Nylon | ??40 | ??MbarS | ??B | ??500 | ??10 | ??1400 | ??-4 | ?7.0E-005 | ????3.7 |
| PET/ is flat | ??48 | ??MOS | ??B | ??500 | ??12 | ??1850 | ??-4 | ?7.0E-005 | ????2.2 |
| The PET/ chemistry | ??48 | ??MOS | ??B | ??500 | ??12 | ??1975 | ??-4 | ?7.0E-005 | ????2 |
| The PET/ chemistry | ??48 | ??MOS | ??B | ??500 | ??12 | ??1100 | ??-4 | ?7.0E-005 | ????3 |
| ??OPP | ??70 | ??MOS | ??B | ??500 | ??12 | ??1100 | ??-4 | ?7.0E-005 | ????3 |
Therefore, the present invention can also make film efficiently with low cost.Generally, adopt method of plasma processing of the present invention that planar film is metallized, rather than use the film of special formulation, can save at least 15%.For example, table 2 and table 3 show that some modal values of the film of employing the present invention preparation are thereafter the metallized film of past of 5 mil thickness and the value of transparent film barrier below.
| Table 2: oxygen transmission rates (OTR) (cc/100 inch under 75 ℃ and 50%RH 2/ day) | |
| Carry out Cement Composite Treated by Plasma and metallization (according to the present invention) on the two sides | 0.0035 it is or littler |
| Carry out Cement Composite Treated by Plasma and metallization (according to the present invention) in one side | ????0.01-0.025 |
| Metallization PET film | ????0.05-0.08 |
| Metallization OPP | ????0.06-1.0 |
| The clear PET film | ????7-9 |
| Transparent OPP | ????95-130 |
| Transparent nylon | ????2-3.8 |
| Table 3: steam permeating rate (WVTR) (cc/100 inch under 75 ℃ and 50%RH 2/ day) | |
| Carry out Cement Composite Treated by Plasma and metallization (according to the present invention) in one side | ????0.008-0.15 |
| Metallization PET film | ????0.05-0.1 |
| The clear PET film | ????2.8 |
| Transparent OPP film | ????0.5-1.0 |
| Transparent nylon | ????7-11 |
In another better embodiment of the present invention, adopt in this embodiment of three sound zone systems (for example), in first district, carry out online surface treatment (promptly in metallization equipment, carrying out Cement Composite Treated by Plasma) at Galileo Mega2.Like this, can cleaning film, remove defect and impurity, make film reach better metal adhesion, therefore improving barrier properties all is the online above-mentioned effect that reaches.Metallization is carried out in second district, and linear velocity can be up to 3,000fpm.Because this multi-region system, equipment can reach and keep 10
-5The vacuum of mbar scope, this can improve density metal and prevent pore.The all right deposition of aluminum of Mdga2 equipment is used for microwave applications and complete opaque application.The film material cools off in the 3rd district, even when a large amount of metal deposition, also film material temperature can be remained in 2 ℃.This cooling system can move temperature-sensitive and ductile plastics film.And, owing to be three sound zone systems, if desired, can keep different vacuum tightness in each district.For example, the vacuum tightness height of evaporating area, the vacuum tightness of twining the district is low, because of not needing for twining district's high vacuum.
Other factors of improving the thin barrier film performance comprise, regulate this method, carry out Cement Composite Treated by Plasma and metallization and/or carry out one or multi-channel at the one or both sides (" surfaces A " and " surperficial B ") of film.Therefore, though only carry out the result that one metallization just can obtain example, can also use the multiple tracks metallization, improve barrier properties, cost is higher.
In this a series of embodiment, for example, the one side of base material film can metallize on (" metal one side " i.e. table 1 in " MOS "), and carries out Cement Composite Treated by Plasma at the one or both sides (surfaces A or B) of this film.For example, base material film can (surfaces A or B) carry out Cement Composite Treated by Plasma on one surface, carrying out one metallization then on plasma treated face.Perhaps, base material film can carry out Cement Composite Treated by Plasma on surfaces A or B, and then in the surperficial enterprising row metalization through Cement Composite Treated by Plasma, (twice) afterwards again metallize on metallization face.Perhaps, base material film can (before Cement Composite Treated by Plasma) metallize on surfaces A or B, carries out Cement Composite Treated by Plasma then on metallization face, afterwards, metallizes in the metallic surface of Cement Composite Treated by Plasma in (road) again again.Perhaps, base material film can carry out Cement Composite Treated by Plasma on surfaces A or B, in surperficial enterprising row metalization, on metallization face, carry out Cement Composite Treated by Plasma more then, and waiting metallization (twice) once more on the metallized surface that gas ions is handled through Cement Composite Treated by Plasma.
In the embodiment of another series, (" metal both sides " i.e. table 1 in " MBS ") all metallizes on the base material film two sides.For example, base material film can carry out Cement Composite Treated by Plasma on two surfaces A and B, all metallize on each face then (every is passed through once).Perhaps, base material film can only carry out Cement Composite Treated by Plasma on a surface (surfaces A or B), and two enterprising row metalizations in surface (every is passed through once).Perhaps, base material film can carry out Cement Composite Treated by Plasma on two surfaces A and B, and A face and B face be once metallization separately all, and then carries out Cement Composite Treated by Plasma on one side, metallize at same this face (the A face passes through once, and the B face is by twice) again.Perhaps, base material film can be in surfaces A and the enterprising row metalization of B (before carrying out Cement Composite Treated by Plasma), and then, surfaces A or B carry out Cement Composite Treated by Plasma, subsequently in metallize again on the face of Cement Composite Treated by Plasma (one side one, second twice).Perhaps, base material film A face only metallizes, and the B face carries out Cement Composite Treated by Plasma and metallization, and the B face carries out Cement Composite Treated by Plasma and metallization (the A face once passes through, and the B face passes through for twice) once more subsequently.Perhaps, the A face of base material film carries out Cement Composite Treated by Plasma and metallization, and the B face only metallizes at first, and subsequently, the B face carries out Cement Composite Treated by Plasma (on metalized surface), and (A face one, B face twice) then once more metallize.
Equally, can carry out Cement Composite Treated by Plasma and/or metallized arbitrary number or combination at any one or both sides on surface, this is according to the invention.
Therefore, according to the present invention, the superelevation barrier membranes (as polyester, polypropylene, polyethylene, polyvinyl chloride or nylon) of Cement Composite Treated by Plasma can be provided, metallize at the one or both sides of this film, this film can be used for for example food or liquid packaging with low cost, or is used for decorative balloons.See through this processing film that the present invention obtains, its oxygen transport (OTR) is less than the 0.01cc/100 inch
2/ day, be reduced to the 0.02-0.35cc/100 inch in the moisture vapor transfer rate (WVTR) of 100/100%RH
2/ day, even less than the 0.02cc/100 inch
2/ day, look selected base material and different.
For example, use nylon, oxygen transport (OTR) is by the 0.07cc/100 inch of art methods
2/ sky is reduced to the 0.015cc/100 inch
2/ day.Use nylon MBS, OTR is from the 0.070cc/100 inch
2/ sky is reduced to the 0.0025cc/100 inch
2/ day.Use polyester, OTR is from the 0.050-0.070cc/100 inch
2/ sky is reduced to the 0.015-0.030cc/100 inch
2/ day.Its in the moisture vapor transfer rate (WVTR) of 100/100%RH also from the 0.070-0.100cc/100 inch
2/ sky is reduced to the 0.015cc/100 inch
2/ day.Adopt the present invention, metal tackiness (metal adhesion bond) also is increased to 400-500 gram/inch from 250 gram/inches.
And, select to use one or both sides to metallize and/or Cement Composite Treated by Plasma, and carry out one or many Cement Composite Treated by Plasma and/or metallization, barrier properties of the present invention can also be increased to any degree of requirement.Such variation is more effective, but cost increases.Therefore, though the barrier properties of listing above is the representativeness that obtains with relatively low cost,, if desired, can obtain even better permeability barrier according to the present invention.
The better thickness of metalized film can be selected thickness according to the rigidity of the required packing instructions of the finished product in the 0.20-10 mil.At one preferably in the embodiment, metalized film also usefulness be the flat plastic film, this film has carried out Cement Composite Treated by Plasma at its one or both sides, and metallizes at its one or both sides.The substrate surface of film can also carry out chemical treatment or corona treatment before carrying out Cement Composite Treated by Plasma or metallization.For example, can use Materials, Inc.of Covington, the chemical treatment SP91 film of Georgia or SP95 film available from SKC.The gas that is used for Cement Composite Treated by Plasma can be argon gas, nitrogen and/or the oxygen of different ratios, or the mixture of other desired gas.
Although described the present invention in conjunction with some embodiments, should be understood that these descriptions are not construed as limiting, because can propose further change, perhaps these further change and it will be apparent to those skilled in the art that.The application is intended to cover all these changes and improvement.
Claims (80)
1. method that comprises the following steps,
Be provided for the material of food or liquid packaging, described material comprises a kind of plastics film, described plastics film has carried out Cement Composite Treated by Plasma in the vacuum chamber of metallization equipment, on the one side at least of plastics film, apply the metal that requires, form metallized film, the oxygen transmission rates (OTR) of described metallized film is not more than the 0.03cc/100 inch
2/ day, the steam permeable speed under 100 and 100%RH is not more than the 0.035cc/100 inch
2/ day.
2. the method for claim 1 is characterized in that, described metal is an aluminium.
3. the method for claim 1 is characterized in that, described metal is a silver.
4. the method for claim 1 is characterized in that, described metal is a gold.
5. the method for claim 1 is characterized in that, described metal is a tin.
6. as each described method among the claim 1-5, it is characterized in that described plastics film is a polyester.
7. as each described method among the claim 1-5, it is characterized in that described plastics film is a polypropylene.
8. as each described method among the claim 1-5, it is characterized in that described plastics film is a polyethylene.
9. as each described method among the claim 1-5, it is characterized in that described plastics film is a polyvinyl chloride.
10. as each described method among the claim 1-5, it is characterized in that described plastics film is a nylon.
11., it is characterized in that described Cement Composite Treated by Plasma is used at least two kinds of mixtures that are selected from following gas: nitrogen, argon gas and oxygen as each described method among the claim 1-10.
12., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of nitrogen and argon gas as each described method among the claim 1-10.
13., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of 80% nitrogen and 20% argon gas as each described method among the claim 1-10.
14., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of oxygen and argon gas as each described method among the claim 1-10.
15., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of 30% oxygen and 70% argon gas as each described method among the claim 1-10.
16., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of 50% oxygen and 50% argon gas as each described method among the claim 1-10.
17., it is characterized in that described oxygen transmission rates is the 0.01-0.03cc/100 inch as each described method among the claim 1-16
2/ day.
18., it is characterized in that described oxygen transmission rates is no more than the 0.01cc/100 inch as each described method among the claim 1-16
2/ day.
19., it is characterized in that described oxygen transmission rates is no more than the 0.0035cc/100 inch as each described method among the claim 1-16
2/ day.
20., it is characterized in that described oxygen transmission rates is no more than the 0.0025cc/100 inch as each described method among the claim 1-16
2/ day.
21., it is characterized in that under 100 and 100%RH, described steam permeable speed is the 0.02-0.035cc/100 inch as each described method among the claim 1-16
2/ day.
22., it is characterized in that under 100 and 100%RH, described steam permeable speed is no more than the 0.02cc/100 inch as each described method among the claim 1-16
2/ day.
23., it is characterized in that under 100 and 100%RH, described steam permeable speed is no more than the 0.015cc/100 inch as each described method among the claim 1-16
2/ day.
24., it is characterized in that described plastics film simultaneously metallizes at it as each described method among the claim 1-23.
25., it is characterized in that described plastics film metallizes on its two sides as each described method among the claim 1-23.
26., it is characterized in that described plastics film simultaneously carries out Cement Composite Treated by Plasma at it as each described method among the claim 1-23.
27., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma on its two sides as each described method among the claim 1-23.
28., it is characterized in that described plastics film at least simultaneously carries out at least twice metallization at it as each described method among the claim 1-23.
29., it is characterized in that described plastics film at least simultaneously carries out at least twice Cement Composite Treated by Plasma at it as each described method among the claim 1-23.
30., it is characterized in that described plastics film has carried out at least twice metallization and at least twice Cement Composite Treated by Plasma as each described method among the claim 1-23.
31., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma and metallizes at its first face as each described method among the claim 1-23.
32., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma at its first face, metallizes at first face subsequently, metallizes at first face again as each described method among the claim 1-23.
33., it is characterized in that described plastics film metallizes at its first face, carries out Cement Composite Treated by Plasma at first face subsequently, metallizes at first face again as each described method among the claim 1-23.
34., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma at its first face, metallizes at first face subsequently, carries out Cement Composite Treated by Plasma at first face again, metallizes again as each described method among the claim 1-23.
35., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma on its two sides, metallizes on the two sides then as each described method among the claim 1-23.
36., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma at its first face, metallizes on the two sides then as each described method among the claim 1-23.
37. as each described method among the claim 1-23, it is characterized in that, described plastics film carries out Cement Composite Treated by Plasma and metallization at its first and second face, described Cement Composite Treated by Plasma and metallization are carried out once with any order, carry out Cement Composite Treated by Plasma at first face subsequently, metallize at first face again.
38., it is characterized in that described plastics film metallizes at its first and second face, carries out Cement Composite Treated by Plasma at its first face subsequently, metallizes again as each described method among the claim 1-23.
39. as each described method among the claim 1-23, it is characterized in that, described plastics film metallizes at its first face, metallize and Cement Composite Treated by Plasma at its second face, carry out Cement Composite Treated by Plasma and the second metallization second time at its second face subsequently, described second time, Cement Composite Treated by Plasma and second metallization can arbitrary order carry out.
40. as each described method among the claim 1-23, it is characterized in that described plastics film carries out Cement Composite Treated by Plasma and metallization at its first face, metallize at its second face, carry out Cement Composite Treated by Plasma at second face subsequently, metallize at second face again.
41. method that comprises the following steps:
The material that is used for making decorative balloons is provided, described material comprises a kind of plastics film, described plastics film has carried out Cement Composite Treated by Plasma in the vacuum chamber of metallization equipment, one side at least at described film applies the metal that requires, form the metallized plastic film, the oxygen transmission rates (OTR) of described metallized plastic film is not more than the 0.03cc/100 inch
2/ day, the steam permeable speed under 100 and 100%RH is not more than the 0.035cc/100 inch
2/ day.
42. method as claimed in claim 41 is characterized in that, described metal is an aluminium.
43. method as claimed in claim 41 is characterized in that, described metal is a silver.
44. method as claimed in claim 41 is characterized in that, described metal is a gold.
45. method as claimed in claim 41 is characterized in that, described metal is a tin.
46., it is characterized in that described plastics film is a polyester as each described method among the claim 41-45.
47., it is characterized in that described plastics film is a polypropylene as each described method among the claim 41-45.
48., it is characterized in that described plastics film is a polyethylene as each described method among the claim 41-45.
49., it is characterized in that described plastics film is a polyvinyl chloride as each described method among the claim 41-45.
50., it is characterized in that described plastics film is a nylon as each described method among the claim 41-45.
51., it is characterized in that described Cement Composite Treated by Plasma is used at least two kinds of mixtures that are selected from following gas: nitrogen, argon gas and oxygen as each described method among the claim 41-50.
52., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of nitrogen and argon gas as each described method among the claim 41-50.
53., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of 80% nitrogen and 20% argon gas as each described method among the claim 41-50.
54., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of oxygen and argon gas as each described method among the claim 41-50.
55., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of 30% oxygen and 70% argon gas as each described method among the claim 41-50.
56., it is characterized in that described Cement Composite Treated by Plasma is used the mixture of 50% oxygen and 50% argon gas as each described method among the claim 41-50.
57., it is characterized in that described oxygen transmission rates is the 0.01-0.03cc/100 inch as each described method among the claim 41-56
2/ day.
58., it is characterized in that described oxygen transmission rates is no more than the 0.01cc/100 inch as each described method among the claim 41-56
2/ day.
59., it is characterized in that described oxygen transmission rates is no more than the 0.0035cc/100 inch as each described method among the claim 41-56
2/ day.
60., it is characterized in that described oxygen transmission rates is no more than the 0.0025cc/100 inch as each described method among the claim 41-56
2/ day.
61., it is characterized in that under 100 and 100%RH, described steam permeable speed is the 0.02-0.035cc/100 inch as each described method among the claim 41-56
2/ day.
62., it is characterized in that under 100 and 100%RH, described steam permeable speed is no more than the 0.02cc/100 inch as each described method among the claim 41-56
2/ day.
63., it is characterized in that under 100 and 100%RH, described steam permeable speed is no more than the 0.015cc/100 inch as each described method among the claim 41-56
2/ day.
64., it is characterized in that described plastics film simultaneously metallizes at it as each described method among the claim 41-63.
65., it is characterized in that described plastics film metallizes on its two sides as each described method among the claim 41-63.
66., it is characterized in that described plastics film simultaneously carries out Cement Composite Treated by Plasma at it as each described method among the claim 41-63.
67., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma on its two sides as each described method among the claim 41-63.
68., it is characterized in that described plastics film at least simultaneously carries out at least twice metallization at it as each described method among the claim 41-63.
69., it is characterized in that described plastics film at least simultaneously carries out at least twice Cement Composite Treated by Plasma at it as each described method among the claim 41-63.
70., it is characterized in that described plastics film has carried out at least twice metallization and at least twice Cement Composite Treated by Plasma as each described method among the claim 41-63.
71., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma and metallizes at its first face as each described method among the claim 1-23.
72., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma at its first face, metallizes at first face subsequently, metallizes at first face again as each described method among the claim 41-63.
73., it is characterized in that described plastics film metallizes at its first face, carries out Cement Composite Treated by Plasma at first face subsequently, metallizes at first face again as each described method among the claim 41-63.
74., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma at its first face, metallizes at first face subsequently, carries out Cement Composite Treated by Plasma at first face again, metallizes again as each described method among the claim 41-63.
75., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma on its two sides, metallizes on the two sides then as each described method among the claim 41-63.
76., it is characterized in that described plastics film carries out Cement Composite Treated by Plasma at its first face, metallizes on the two sides then as each described method among the claim 41-63.
77. as each described method among the claim 41-63, it is characterized in that, described plastics film carries out Cement Composite Treated by Plasma and metallization at its first and second face, described Cement Composite Treated by Plasma and metallization are carried out once with any order, carry out Cement Composite Treated by Plasma at first face subsequently, metallize at first face again.
78., it is characterized in that described plastics film metallizes at its first and second face, carries out Cement Composite Treated by Plasma at its first face subsequently, metallizes again as each described method among the claim 41-63.
79. as each described method among the claim 41-63, it is characterized in that, described plastics film metallizes at its first face, metallize and Cement Composite Treated by Plasma at its second face, carry out Cement Composite Treated by Plasma and the second metallization second time at its second face subsequently, described second time, Cement Composite Treated by Plasma and second metallization can arbitrary order carry out.
80. as each described method among the claim 41-63, it is characterized in that described plastics film carries out Cement Composite Treated by Plasma and metallization at its first face, metallize at its second face, carry out Cement Composite Treated by Plasma at second face subsequently, metallize at second face again.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/403,294 | 2002-08-13 | ||
| US40329502P | 2002-08-14 | 2002-08-14 | |
| US44885903P | 2003-02-21 | 2003-02-21 | |
| US60/448,859 | 2003-02-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1685076A true CN1685076A (en) | 2005-10-19 |
| CN100457959C CN100457959C (en) | 2009-02-04 |
Family
ID=31949851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038231662A Expired - Fee Related CN100457959C (en) | 2002-08-14 | 2003-08-14 | Plasma treated metallized films |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100457959C (en) |
| AU (2) | AU2003262703A1 (en) |
| WO (1) | WO2004016417A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106480406A (en) * | 2016-10-17 | 2017-03-08 | 东丽薄膜加工（中山）有限公司 | Metallized film and preparation method thereof and capacitor |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0208506D0 (en) | 2002-04-12 | 2002-05-22 | Dupont Teijin Films Us Ltd | Film coating |
| EP1634699A1 (en) * | 2004-09-10 | 2006-03-15 | Syrom 90 S.P.A. | Multilayer metallized film and production method |
| US7799399B2 (en) * | 2006-06-07 | 2010-09-21 | Toray Plastics (America), Inc. | High barrier laminate and process |
| US9186593B2 (en) | 2006-06-07 | 2015-11-17 | Toray Plastics (America), Inc. | Stretchable and formable lighter than air balloons made from a biaxially oriented polyester film |
| US8399080B2 (en) | 2006-06-07 | 2013-03-19 | Toray Plastics (America), Inc. | Lighter than air balloon made from a biaxially oriented polyester film |
| EP2222459A4 (en) * | 2007-12-10 | 2012-12-05 | Toray Plastics America Inc | Biaxially oriented polylactic acid film with high barrier |
| ITRM20080449A1 (en) * | 2008-08-08 | 2010-02-09 | Michele Colajanni | PLASTIC SHEET LAMINATED WITH PRECIOUS METAL |
| EP2323788B1 (en) | 2008-08-15 | 2014-07-30 | Toray Plastics (America) , Inc. | Biaxially oriented polylactic acid film with high barrier |
| US9150004B2 (en) | 2009-06-19 | 2015-10-06 | Toray Plastics (America), Inc. | Biaxially oriented polylactic acid film with improved heat seal properties |
| US9221213B2 (en) | 2009-09-25 | 2015-12-29 | Toray Plastics (America), Inc. | Multi-layer high moisture barrier polylactic acid film |
| US9023443B2 (en) | 2009-09-25 | 2015-05-05 | Toray Plastics (America), Inc. | Multi-layer high moisture barrier polylactic acid film |
| WO2011123165A1 (en) | 2010-03-31 | 2011-10-06 | Toray Plastics (America), Inc. | Biaxially oriented polyactic acid film with reduced noise level |
| US9492962B2 (en) | 2010-03-31 | 2016-11-15 | Toray Plastics (America), Inc. | Biaxially oriented polylactic acid film with reduced noise level and improved moisture barrier |
| AT511420A1 (en) * | 2011-04-21 | 2012-11-15 | Ros Nico | PACKAGING WITH ENCLOSING HEAT BARRIER |
| US9561676B2 (en) | 2011-07-08 | 2017-02-07 | Toray Plastics (America), Inc. | Biaxially oriented bio-based polyester thin films and laminates for thermal transfer printing |
| US10137625B2 (en) | 2011-07-08 | 2018-11-27 | Toray Plastics (America), Inc. | Biaxially oriented bio-based polyester films and laminates |
| US20170368807A1 (en) | 2016-06-28 | 2017-12-28 | Toray Plastics (America), Inc. | Formable polyester films |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3828960A (en) * | 1972-11-10 | 1974-08-13 | Dow Chemical Co | Heat insulating container having plastic walls retaining vacuum |
| EP0705757A1 (en) * | 1994-10-07 | 1996-04-10 | Rhone-Poulenc Inc. | Lighter than air balloons |
| US5981079A (en) * | 1997-01-29 | 1999-11-09 | Mobil Oil Corporation | Enhanced barrier vacuum metallized films |
| US6110599A (en) * | 1997-04-21 | 2000-08-29 | Eastman Chemical Company | Blends of polyethylene for extrusion coating |
-
2003
- 2003-08-14 WO PCT/US2003/025582 patent/WO2004016417A2/en not_active Application Discontinuation
- 2003-08-14 AU AU2003262703A patent/AU2003262703A1/en not_active Abandoned
- 2003-08-14 CN CNB038231662A patent/CN100457959C/en not_active Expired - Fee Related
-
2009
- 2009-10-30 AU AU2009233624A patent/AU2009233624A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106480406A (en) * | 2016-10-17 | 2017-03-08 | 东丽薄膜加工（中山）有限公司 | Metallized film and preparation method thereof and capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003262703A1 (en) | 2004-03-03 |
| AU2009233624A1 (en) | 2009-11-26 |
| WO2004016417A2 (en) | 2004-02-26 |
| CN100457959C (en) | 2009-02-04 |
| WO2004016417A3 (en) | 2004-06-03 |
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